Process of preparing ccif



Patented Sept. 2, 1947 v 2,426,037 p raooass or PREPARING CClFa William s. Murray, Wilmington, Del.,=assignor to E. I. du Pont de Nemours & Company, Wilmington, Del., a corporation of Delaware No Drawing. Application August '7, 1946. Serial No. 688,969

1 This invention relates to a process for preparing CClFa and more particularly to a'continuous vapor phase process for preparing CCIF: from chlorofiuoromethanes containing a smaller proportion of fluorine.

The preparation of CClF3 by prior known processes, such as by fluorination, have been uneconomical. In Patent 1,994,035, it is further disclosed that small amounts of CClFa were obtained in the batchwise liquid phase disproportionation of CClaF to produce CClaFa. Since CClFs is or value for use in low temperature refrigeration, it has become desirable to discover a simple and economical method for making'this compound in high yields.

It is an object of the present invention to provide a novel method for preparing CClFa. Another object is to provide a practical and commercial method for the manufacture of CClFa in high yields. Other objects are to advance the art. Still other objects will appear hereinafter.

The above and other objects may be accomplished in accordance with my invention which comprises passing a substantially anhydrous chlorofluoromethane, consisting of carbon, chlorine and fluorine and containing 2 to 3 chlorine atoms, in the vapor phase through an anhydrous aluminum halide catalyst, in which the halogen is chlorine or bromine, at a rate of from 0.1 pound to 2.5 pounds of the chlorofluoromethane for each pound of aluminum halide per hour while maintaining a temperature of from about 100 C. to about 175 C. in the catalyst. I have found that, by such method, I am able to produce CClFa in excellent'yields and in a simple and economical manner which is practical to employ on a commercial scale.

The chlorofiuoromethanes, which may be employed in this process, are CClzFn and CClaF. Either of these chlorofluorom'ethanes may be employed by itself or I may employ mixtures of the two in any desired proportions. The reactions involved may be simply illustrated by the equations:

. 3CChF: CCll-l-2CC1F:

(2) AlCll a 0015]? 2 001. CClF;

The chlorofluoromethane should be substantially -.anhydrous, that is, should not contain more than about 0.001% by. weight of water, so as to avoid excessive catalyst deterioration by hydrolysis and to minimize the acidity of the product gases.

The catalyst employed may be aluminum chlo-.

16 Claims. (Cl.260-653)- ride or aluminum bromide. The preferred cat alyst isv aluminum chloride. The aluminum halide catalyst should also be subst' ntially anhydrous. Aluminum chloride of commercial grade has been found to be very satisfactory. The

. aluminum halide may be employed without a carrier and should be in the form of coarse particles, as grains, lumps, pieces, etc. 4 mesh to 30 mesh is satisfactory and will usually be desired. For large commercial scale production, it will generally be preferred to have the catalyst particles in a size of from about 4 mesh to about 10 mesh. The catalyst may be supported on an inert carrier, such as silica or alumina by a side reaction which may be represented by the following equation:

3CCl:F2+A1C1a- 2A1Fa+CC14 Such reaction results in a gradual decrease in the catalyst eflqciency, since the AlFa formed therein does not catalyze the desired reaction. This side reaction also results in a consumption of the starting material to produce undesired products. I have found that this side reaction takes place preferentially at low temperatures and with high rates of feed of the chlorofluoromethane. On the other hand, by suitably controlling the conditions, I am able to minimize the side reaction and favor the desired reaction so as to produce high yields of CClFa.

' Iphave found that it is essential to pass the chlorofluoromethane in the vapor phase into contact with the catalyst. The catalyst should be maintained at a temperature of from about C. to about 175 C. and preferably at from about C. to about 135 C. At temperatures substantially below 100 C., the conversion of the starting chlorofluoromethane is small, the yield of CClFa is very low and the life of the catalyst is very short. At temperatures substantially above 175 0., there is a strong tendency for sublimation of the catalyst and control of the reaction becomes impractical. Optimum consumptions, yield and catalyst life are obtained at temperatures of from C. to C. In order to maintain the catalyst temperature and the catalyst life, it will usually be desirable to preheat the starting chlorofluoromethane to substantially the reaction temperature, preferably to about 120 C. to about 135 C.

Catalyst of from tillation.

'3 The chlorofluoromethane should be fed to the catalyst at the rate of from about 0.1 pound to about 2.5 pounds for each pound oi catalyst per hour- Higher rates of feed of the chlorofluoromethane adversely afiect the chloroiluoromethane consumption and the yield of CClFa, render the temperature control difllcult and require excessive recycling of unreacted starting material. Optimum results are obtained with a chlorofluoromethane feed rate of from about 0.19 pound to about 0.5 pound for each pound of aluminum halide per hour.

The process may be operated at pressures of from about pounds to about 150 pounds per square inch absolute. As the pressure is increased, the greater concentration of the reactant gas will result in an increased reaction rate and it becomes necessary to provide for more eflicient dissipation of the heat evolved so that the temperature can be maintained within the desired limits. This may be accomplished by employing known methods, such as reducing the diameter of the catalyst bed, increasing the linear velocity of the gas and the like. Usually, pressures of from about 15 to about 30 pounds per square inch absolute will be employed. Preferably, I employ pressures of about atmospheric pressure, that is, pressures of from about 15 to about 18 pounds per square inch absolute.

The reactor employed may be constructed of suitable inert material, such as glass, copper and steel. The reactor may be heated by any suitable means, such as steam. water, oil and the like.

The gaseous reaction products will usually be passed through a soda lime tower or similar means for removing hydrochloric acid. and traces of moisture in the gases may be removed by passing the gases over silica gel or other suitable drying agent. The CClFa may be recovered fromthe CC14, unreacted chlorofiuoromethan and other products, by fractional condensation or dis- The unreacted chlorofluoromethane and intermediate products may also be separated from the carbon tetrachloride by fractional con densation or distillation and recycled to the process.

In order to more clearly illustrate my invention, preferred modes of carrying the same into' effect and the advantageous results to be obtained thereby, the following examples are given in which the per cent yield of CClF; is calculated on the basis or the starting chlorofluoromethane consumed.

Example I Dichlorodifiuoromethane (dried vapor phase over P205 and preheated to about 120 C.) was fed at 770 mm. of Hg absolute pressure into a 1".copper-reactor containing 5-20 mesh commercial AlCls at the rate of 0.35 1bs./lb.

showed only 0.34% weight of All: in the cat-.-'

alyst.

Catalyst Lire irom Start Analysis of sample, oi CChF: Flow Per Cent oi Theory n. CClF 8 CClF S. on- I Lb. A101: sump- Yield 2 etc 19 as 18.5 a. a 82 as as a. 2 as no as 15 so so 211 31 so 99 439 71. 5 e0 91 Example I! With experimental conditions identical in every other respect to those mentioned under Example I, CClzFz was fed to the reactor at the rate of 0.78 lb.'/lb. AlCla/hour. The catalyst analyzed 34% AlFa at the end of this experiment.

Catalyst Life from Start Analysis of Sample, oi COlnFa Flow Per Cent of Theory Lb CCIF I 08m? CCIF 8. 3 On- Lb. A101. sump- Yield tion These data show the deleterious effect oi short contact time on the catalyst life.

\ Example III Preheated; PzOs -dried CClrFa at atmospheric pressure was fed into a steel reactor, packed with 3.4 lbs. 5-20 mesh AlCls, at the rate of 0.19 lb./lb. AlCla/hour. The catalyst temperature was maintained between 122 and 128 C. by means of 20' p. s. i. g. steam in the reactor Jacket. A consumption of 94% and a yield of 96% of theory 01 C011: was obtained.

Example IV This experiment was run under conditions identical with those reported for Example I, except that, in this case, the reaction temperature was the catalyst contained 10.7% AlFa.

held at 100 C. At the end oi this experiment,

Catalyst Liio irom sum Analysis oi Sample, oi CChF Flow Per Cent oi Theory Lbs CCIFI' 8 00]! I on- Lb. A101. sump- Yield tion as F 0.12 24.5 26 0.81 an so 04 a0 15.4 100 215 0.1 12 as A typical analysis: -Fed'22.4 g. CClzFa. Recov cred 21.9 g. which analyzed 19.4 g. 01 unreacted CChFr, 1.3 g. of high boilers (mainly C014) and 1.2 8. 01' CClFa. This gives a CClzF: consumption of 12% and a CClF: yield of 83% oi theory.

These data show the deleterious effect or low temperature on the catalyst lire.

Example V Trichloromonoiluoromethane phase over P205) under about atmospheric pres- (dried vapor sure was passed at the rate of 0.32 lb./lbl of catalyst/hr. through a bed of 7-12 mesh AlCla contained in a jacketed copper tube and maintained at 126 C. The composition of the product was as follows:

Weight'per cent CChF' 10 CClzFz 26 CClFa 12 CCl4 '52 the CClzF-z disappeared in a single pass and the yield of CClFa was 95% of theory.

It will be understood that the preceding examples are given for illustrative purposes solely and that my invention is not to be restricted to the specific embodiments disclosed, but that many variations and modification can be made without departing from the spirit or scope of my '6 fluoromethane, consisting of carbon, chlorine and fluorine and containing 2 to 3 chlorine atoms, in the yapor phase through an anhydrous aluminum ,halide- 'catalyst, in which the halogen is a'member of the group consisting of chlorine and bromine, at a rate of from 0.1 pound to 2.5 pounds of chlorofluoromethane for each pound of aluminum halide per hour while maintaining a temperature of from about 120 C. to about 135 C. in the catalyst and then separating CClFa from the reaction mixture.

3. The process of preparing CClFa. which comprises passing a substantially anhydrous chloroinvention. For example, the tempratures and rates of flow may be varied within the limits given. Mixtures of aluminum chloride and' of obtaining better heat transfer in two reactors than with a single reactor. Also, various other methods may be employed for separating the products.

It will be seen that, by my invention, I have provided a simple and economical method of obtaining CClF: in high yields by a continuous vapor phase disproportionation of chlorofluoromethanes, containing a lower concentration of fluorine, in the presence of aluminum halides. By suitable control of the conditions within the preferred range, I am able to obtain consumptions of chlorofluoromethane of at least 90%, yields of CCIF: of at least 98% and a catalyst life in excess of '15 pounds of CClF; per pound of aluminum halide. Thus, it will be apparent that. by my invention, I have made a very substantial advance in the art.

I claim:

1. The process of preparing CCIF: which comprises passing a substantially anhydrouschlorofluoromethane, consisting of carbon, chlorine and fluorine and containing 2 to- 3 chlorine atoms, in the vapor phase through an anhydrous aluminum halide catalyst, in which the halogen is a member of the group consisting of chlorine and bromine, at a rate of from 0.1 pound to 2.5 pounds of chlorofluoromethane for each pound of aluminum halide per hour while maintaining a temperature of from about 100 C. to about 175 C. in the catalyst and then separating CClFa from the reaction fluoromethane, consisting of carbon, chlorine and fluorine and containingZ to 3 chlorine atoms, in the vapor phase through an anhydrous aluminum halide catalyst, in which the halogen is a member of the'group consisting of chlorine and bromine, at a rate of from about 0.19 pound to about 0.5 pound of chlorofluoromethane for each pound of aluminum halide per hour while maintaining a temperature of from about C. to about'135" C. in the catalyst and then separating CClF; from the reaction mixture.

4. The process of preparing CClF'a which comprises passing a substantially anhydrous chlorofiuoromethane, consisting of carbon, chlorine and.

fluorine and containing 2 to 3 chlorine atoms, in the vapor phase at about atmospheric pressure through an anhydrous aluminum halide catalyst, in which the halogen is a member of the group consisting of chlorine and bromine, at a rate of from about 0.19 pound to about 0.5 pound or ch10- rofluoromethane for each pound of aluminum halide per hour while maintaining a temperature of from about 120 C. to about C. in the catalyst and then separating CCIF: from the reaction mixture. 7

5. The process of preparing CClFa which comprises passing substantially anhydrous dichlorodifluoromethane in the vapor phase through an anhydrous aluminum halide catalyst, in which the halogen is a member of the group consisting of chlorine and bromine, at a rate of from 0.1pound' 6. The process of preparing CClFs which com- I prises passing substantially anhydrous dichlorodifiuoromethane in the vapor phase through an anhydrous aluminum halide catalyst, in which the halogen is a member of the group consisting of chlorine and bromine, at a rate of from 0.1 pound to 2.5 pounds of dichlorodiiiuoromethane for each pound of aluminum halide per hour while maintaining a temperature of from about 120 C. to about 135 C. in the catalyst and then separating CClFa from the reaction mixture.

7. The process of preparing CCiF; which comprises passing substantially anhydrous dichlorodlfluoromethane in the vapor phase through an anhydrous aluminum halide catalyst, in which the halogen is a member of the group consistin of chlorine and bromine, at a rate of from about 0.19 to about 0.5 pound of dichlorodifiuoromethane for each pound of aluminum halide per hour while maintaining a temperature or from about 120 C. to about 135 C. in the catalyst and then separating CClF: from the reaction mixture.

8. The process of preparing CClF: which comprises passing substantially anhydrou dichlorodifluoromethane in the vapor phase at about atmospheric pressure through an anhydrous alu- 7 minum halide catalyst, in which the halogen is a member of the group consisting of chlorine and bromine, at a rate of from about 0.19 pound to about 0.5 pound of dichlorodifluoromethane for each pound of aluminum halide per hour while maintaining a temperature of from about 120 C. to about 135 C. in the catalyst and then separating CClFa from the reaction mixture.

9. The process of preparing CCIF: which comprises passing substantially anhydrous dichlorodifluoromethane in the vapor phase through anhydrous aluminum chloride at a rate of from 0.1 pound to 2.5 pounds of dichlorodifluoromethane for each pound of aluminum chloride per hour while maintaining a temperature of from about 100 C. to about 175 C. in the aluminum chloride and then separating CClFa from the reaction mixture. Y

10. The process of preparing CClF: which comprises passing substantially anhydrous dichlorodifluoromethane in the'vapor phase through anhydrous aluminum chloride at a rate of from 0.1 pound to 2.5 pounds of dichlorodifluoromethane for each pound of aluminum chloride per hour while maintaining a temperature of from about 120 C. toabout 135 C. in the aluminum chloride and then separating CCIF: from the reaction mixture.

11. The process of preparing CClFa which comprises passing substantially anhydrous dichlorodifluoromethane in the vapor phase through anhydrous aluminum chloride at a rate of from about 0.19 pound to about 0.5 pound of dichlorodifluoromethane for each pound of aluminum chloride per hour while maintaining a temperature of from about 120 C. to about 135 C. in the and then separating CClFa from the reaction mixture. 13. The process of preparing CClFs which comprises passing substantially anhydrous trichloromonofluoromethane. in th vapor phase through 7 an anhydrous aluminum halide catalyst, in

which the halogen is a member of the group consisting of chlorine and bromine, at a rate of from 0.1 pound to 2.5 pounds of trichloromonofluorov methane for each pound of aluminum halide per hour while maintaining a temperatureof from about C. to about 175 C. in the catalyst and then separating CCIF: from the reaction mixture. v v

14. The process of preparingCClFa which comprises passing substantially anhydrous trichloromonofluoromethane in th vapor phase through an anhydrous aluminum halide catalyst, in which the halogen is a member of the group consisting of'chlorine and bromine, ata rate of from about 0.19 pound to about 0.5 pound of trichloromonofluoromethane for each pound of aluminum halide per hour while maintaining a temperature of from about C. to-about C. in the catalyst 16. The process of preparing CClFawhich comprises passing substantially anhydrous trichloromonofluoromethane in the vapor phase through anhydrous aluminum chloride at a rate of from about 0.19 pound toabout 0.5 pound of'trichloromonofluoromethane for each pound of aluminum cholride per hour while maintaining a temperature of from about 120 C. to about 135 C. in the aluminum chloride and then separating CCiFa from the reaction mixture.

WILLIAM S. MURRAY. 

